Colored glass compositions

ABSTRACT

Colored silicate glass compositions particularly in the form of frit containing chromium oxide and manganese oxide and wherein the ratio of manganese to chromium is expressed on the basis of a weight ratio of manganous oxide, MnO, to chromic oxide, Cr2O3, and ranges from 13.6:1 to 1:1. The compositions can be used for manufacturing a variety of glass articles of commerce and may be used as frit colorant additions for coloring essentially colorless base glasses.

United States Patent [191 Schaller Oct. 28, 1975 COLORED GLASSCOMPOSITIONS [75] Inventor: Arnold L. Schaller, New Orleans,

[73] Assignee: Owens-Illinois, Inc., Toledo, Ohio 22 Filed: Mar. 30,1972 [21] Appl. No.: 239,723

Related US. Application Data [63] Continuation of Ser. No. 883,230, Dec.8, 1969,

OTHER PUBLICATIONS Weyl, W. Coloured Glasses-Sheffield Eng, 1951 pp.116-117, 123,130-131, 136-137.

Volf, M. Technical Glasses(l96l) London, pg. 438. Ceramic Industry-1967Handbook of Materials for Ceramic Processing, p.150 Cerium Oxide, Jan.1967. I

Primary Examiner-Winston A. Douglas Assistant Examiner.lohn F. NieblingAttorney, Agent, or FirmRichard B. Dence; E. J. Holler [5 7 AB STRACTColored silicate glass compositions particularly in the form of fritcontaining chromium oxide and manganese oxide and wherein the ratio ofmanganese to chromium is expressed on the basis of a weight ratio ofmanganous oxide, MnO, to chromic oxide, Cr O and ranges from 13.6:1 to1:1. The compositions can be used for manufacturing a variety of glassarticles of commerce and may be used as frit colorant additions forcoloring essentially colorless base glasses.

14 Claims, No Drawings COLORED GLASS COMPOSITIONS REFERENCE TO A RELATEDAPPLICATION This application is a continuation of my copendingapplication Ser. No. 883,230, filed Dec. 8, 1969 and now abandoned, theentire disclosure of which is relied BACKGROUND OF THE INVENTION Thepresent invention relates to colored glass compositions containingsilica which are suitable for manufacturing colored glass articles ofcommerce and science, and, especially, for use as colorant fritadditions to essentially colorless base glass.

Colored glass compositions are needed in the glass art that possessutility for fabricating colored glass articles and also possess utilityas colorant frits for addition to a colorless base glass to form coloredglasses which in turn are suitable for fabricating colored glassarticles. The present invention satisfies this need by making availableto the art certain glass compositions as described hereinafter.

The glass compositions of the invention are formulated from a uniquemixture of select reagents to pro'- duce colored glasses suitable fordirect use and for use as a colorant glass frit. Glass compositions ofthis invention have important advantages over the prior art glassesbecause small batches can be made of the colored glass compositions formanufacture of colored glass articles on a limited scale; or, ifdesired, a colorant frit can be prepared for addition to and admixturewith a molten stream of a clear base glass.

Frit addition, as is known in the art, is accomplished by flowing aclear base glass from a glass furnace through a forehearth channel,mixing in the frit and withdrawing the composite newly formed coloredglass from the forehearth channel to form glass mold charges. The moldcharges are used in the manufacture of shaped glass articles such ascolored glass bottles, colored drinking glasses, colored ashtrays andthe like.

The colorant glass frit used in the forehearth addition techniquegreatly facilitates and expedites making changes in the color of theulitmate glass. Thus, the forehearth technique makes it possible toeffect a change in color in a matter of a few hours instead of the longperiods of time required for changing of colors in the glass meltingfurnace.

Prior to this invention, the frit available for simulating certaincolors, for example, amber, from colorless flint type glasses were fritscontaining as colorants iron oxides and manganese oxides whichinherently limited the usefulness of said frit.

Accordingly, it is an immediate object of the present invention toovercome the limitations and shortcomings associated with the prior artcompositions of matter.

Another object of the present invention is to provide novel glasscompositions suitable for making glassware.

Yet another object of the invention is to provide a colorant fritcomposition for adding to a base glass.

Yet still a further object of this invention is to provide a variety ofcolored glasses from a colorless glass by the addition of a colorantfrit to the base glass.

These and other objects, features and advantages of the presentinvention will become readily apparent to one skilled in the art fromthe following detailed description thereof.

SUMMARY OF THE INVENTION The invention concerns glass compositionsconsisting essentially of:

Percent by Weight SiO 42 to 56 Fe O 0.5 to 1.5 CaO 0.1 to l MgO 0 to 0.5Na,0 15 to 25 K 0 1.0 to 1.5 Cr O [.5 to 2.8 MnO 12 to 30 CeO 1.5 to 2.8

' In another embodiment, the glasses of the invention consistessentially of:

Percent by Weight SiO 42 to 56 Al O; 0.1 to 0.5 Fe O 0.5 to 1.5 CaO 0.1to l MgO 0 to 0 5 Na- O l5 to 25 K 0 l to 5 MnO 12 to 30 CeO l to 2.5 CrO 1.5 to 2.8 La O 0.1 to 0.5 F O.l to 0.2 BaO 0.01 to 0.1 Pr O 0.01 to0.1 Nd O 0.01 to 0.2

In a still further embodiment, the glasses of the invention consistessentially of:

Percent by Weight SiO 65 to ge g 0(1) to 2.5

a to MgO 0 to 0.3 Na O 15 to 25 K 0 l to 2 v 3' 0; 1.5 to 2.8

n0 2 to 8 A1 0: 0 to 0.2 CrO 0 to 0.4

DETAILED DESCRIPTION OF THE INVENTION 7 compositions. The dombination ofchromium and manganese yields glasses of various colors or shades ofglasses from yellow-amber through amber, purple and black. The presentglasses use chrome oxide, CrO i.e., the hexavalent form of chromium, asan oxidizing agent for manganeseoxide, to keep manganese oxide in afully oxidized state, Mn O The ratio of the chromium oxides andmanganese oxides in the glasses is from a ratio of 13.6/1 to 1/1wherein-manganese is expressed as MnO over chromium with the chromiumexpressed as Cr O Exemplary of specific ratios of glass melts are theratio of MnO/Cr O which was 13.6/1; 9.23/1; 6.2/1; 4/1; 2/1; 1.75/1;1.5/1; and l/l. In most of the melts prepared, the concentration of theCr O was held at a range of 1.5 to 2.8%. with the usual amount of 2.0%used for the average melt.

Exemplary of glasses prepared within the spirit of the present inventionare the following:

A glass containing:

Percent by Weight 810: 42 to 56 Pe s); 0.5 to 1.5 Ca 0.1 to 1 5 0.0 m0.5 Na O 15 to 25 K 0 l to 1.5 Cr O 1.5 to 2.8 MnO 12 to 30 CeO 1.5 to2.8

A glass consisting essentially of:

Percent by Weight SiO 42 to 56 A1 0: 0.1 to 0.5 Fe O 0.5 to 1.5 CaO 0.1to l MgO o to 0.5 Na O 15 to 25 K 0 1 t0 5 MnO 12 to 30 CeO; 1 to 2.5C1110; 1.5 to 2.8 Lil- 0 0.1 to 0.5 F 0.1 to 0.2 8:10 0.01 to 0.1 Pr o0.01 to 0.1 Nd O 0.01 to 0.2

A glass consisting essentially of:

Percent by Weight SiO 65 to 75 Fe O; 0.1 to 0.5 CaO O to 4 MgO 0 to 0.3N3 0 15 to 25 K 0 l to 2 Cr O; 1.5 to 2.8 MnO 2 to 8 A1 0 0 to 0.2 CrO 0to 0.4

Generally, when frits were desired, the frit samples were about 200grams batch weight and they were melted in a platinum crucible for aboutone hour at 2400 F. in an air atmosphere. In large production runs, themelt was in an electric furnace, and the temperature as measured in therefiner was about 2300 to 2500 F. The atmosphere of the refiner of thefurnace was approximately neutral. Some samples were melted for varyingperiods of time to determine if prolonged melting destroyed the color.For example, some sample melts were melted in a drop hearth electricfurnace for periods of one-half hour to 12 hours. The sample glass wasthen fritted or crushed and added to a commercially available fiintglass and remelted for threequarter hours to 24 hours. The sample wasthen poured and annealed. There was no loss of color in the desiredglasses as a result of the heating for prolonged times. The generalmelting conditions and procedures for making molten glass areconventional and such conditions are well known to those skilled in theart as set forth in Tooleys Handbook of Glass Manufacturing,

Ogden Publishing Company, New York 36, NY. 1953 at pages 242-245.

EXAMPLES OF SPECIFIC BATCH AND SPECIFIC GLASSES The following batchingredients were used to form a composite glass:

All the ingredients used for preparing the glass are commerciallyavailable. The cerium concentrate, when used for making a glass, isavailable from the Molybdenum Corporation and, in addition to CeO itcontains La O F, BaO, Pr O A1 0 and Nd O It will be apparent from theabove that the cerium concentrate is an optional ingredient. The amountspresent are set forth in the reported analysis. The manganese ore isavailable from the Calumite Company and it often contains trace amountsof SiO Fe O A1 0 and CaO in addition to the MnO. The amounts present areset forth in the glass.

The theoretical glass composition which was produced by melting theabove batch is as follows:

The glass has a theoretical ratio of MnO/Cr O of 13.6. It will be seenfrom the above that this ratio is arrived at by dividing the weightpercent MnO by the weight percent Cr O on a theoretical basis. Thus, theratio is a weight percent ratio. As will be apparent from the exampleshereinbelow, the ratio of MnO/Cr O set forth in each of the followingexamples, is obtained as explained above. The glass can be charged intoa glass forming mold for making an article of manufacture, such as apressed ash tray, or the glass can be employed as a frit and added to aflint glass and then charged into a glass forming mold for making anarticle such as a bottle or the like.

EXAMPLE 2 Another glass prepared according to the spirit of theinvention is as follows:

Ingredients P d Ingredients Pounds Sand 2000 Sand 2000 Soda ash 1473Soda ash 893 Cerium concentrate (CeO 155 ga ese Q e 312 Manganese r (Mo) 1200 Potassium dlchromate I06 Potassium dichromate 176 Thetheoretical composition of the glass prepared The theoreticalcomposition of the above glass was as from this batch is as fOlIOWSIfollows:

Ingredients Percent Ingredients Percent sioz I I 693 1 5 F73 0 0.36 i z49.70 CaO .ji 1 -:--0.41 Fe O 0.95 MgO "i j i 0.16 CaO 0.60 Na O 1 8.26MgO 0.11 K :1.20 Na O 20.96 Z a K20 1 38 MnO 7.74 cr o 2.28 20 MnO 2073C602 Th 1 h 1 h 1 M o/c 0 r f 4 A120: 030 1s g ass a a t eoretlca r1 r 3ra 1o 0 L 0 .34 S 8 EXAMPLE 5 gig 8:8; In the present example, thefollowing batch reagents M1 0 0.16 were prepared for forming a glass:

The glass had a theoretical ratio of MnO/Cr O of ingredients Pmmds Sand2000 Soda ash 893 EXAMPLE 3 Lime 87 Manganese ore 156 The followingcommercially available reagents were Potassium dichromate I06 blendedtogether for preparing a composition of matter:

This glass had a theoretical MnO/Cr O ratio of 2.0 and a theoreticalcomposition as follows: ingredients Pounds Sand 2000 Ingredients PercentSoda ash 1473 Cerium concentrate 155 SiO 72.80 Manganese ore 800 Fc o0.19 Potassium dichromate 176 C80 2.08 MgO 0.17 Na O 18.79 K20 1.23 Thetheoretical composition of the glass prepared 1 3 1.99 MnO 3.98 fromthis batch is as follows:

ingredients Percent EXAMPLE 6 SiO 53.45 F O 0.69 C220 3 049 IngredientsPounds MgO 0.12 N3 0 22.78 Sand K20 50 Soda ash 893 C1305 2.43 i 174 Mno1501 anganese ore 78 ceo 2 48 Potassium dichromate 106 2 A120; 0.22 La o0.37 3 3 This batch gave a glass with a theoretical MnO/Cr O ig ratio ofl and the glass with composition as follows: N0 0, 0.17

ingredients Percent The glass had a MnO/Cr O ratio of 6.2. sioz 7H4 Fe O0.10 EXAMPLE 4 C210 3.80 MgO 0.19

A glass was prepared from the following: a20 18.88

-Continued -Continued Ingredients Percent Ingredients o nds K20 1.24Feldspar 207.5 Cr O 2.00 Lime 332.5 MriO 2.00 5 Salt cake 6.6

Niter 0.24

EXAMPLE 7 The final melt glass, prepared from the above batch, Thefollowing example further demonstrates the 10 conslsts of the followmgOxldes: spirit of the invention:

Ingredients Percent Ingredients Pounds Sio2 7205 TO 0.02 Sand 2000 1 50.001 Soda ash 1046.7 A120:l 1 72 Manganese ore 146.7 p o 0 04 Potassiumdichromate 133.3 o 1 1 99 MgO 0.45 0121 0 13.33 K 0 0.35 This batch gavea glass with a theoretical MnO/Cr o p 0 0002 ratio of 1.5 and acomposition as follows:

A frit was added to the above glass to produce an oxilng'ed'ems Percentdized amber glass by forehearth addition technique. $02 7006 The coloredflint glass produced was molded by conlzga 0.06 ventional glasstechniques into glass bottles. The frit 83?, glass used for thisproduction run consists essentially of Na o 21.57 70.06 weight percentSiOi 0.06 weight percent A1 0 2% 0.33 weight percent CaO; 0.16 weightpercent MgO; 0:0: 2: 5 21.57 weight percent Na O; 1.52 weight percent K0; Mno 0.17 wei ht ercent Fe O 2.45 wei ht ercent Cr O g g P and 3.67weight percent MnO.

As will be apparent from the foregoing examples, EXAMPLE 3 thosecompositions which are made from batch ingredients not includin thecerrium concentrate of Exam 1e A base flint glass was prepared by mixingand melting p 1, have the following range of ingredients. batch setforth immediately below:

Ingredients Weight Percent Ingredients Pounds 40 510 69.8 728 Sand 19899F8203 0.10 0.36 Soda ash 656.0 o 33 3 30 Blast furnace slag 80.0 o (1160 19 Feldspar 2140 N3 0 18.26 21.57 Lime 593-0 K 0 1.20 1.52 Salt cake15.0 CH03 1 94 245 Ni er (N N i) 048 MriO 2.00 7.74 A1203 0 0.06

A glass produced from the above batch was mixed with a fritted glass,remelted for three-quarter hours to Th6 foregoing ranges are based onEXamPIeS 6 give an amber color glass. The frit added to the flint and TIt W111 be Seen from Examples 6 and 7 that glass consists of 70.06percent by weight SiO 0.06 the ratlO 0f z a ranges from 1 to percent byweight A1 0 0,33 er t b i ht (3 0; Compositions of the foregoingexamples prepared 0.16 percent by weight MgO; 21.57 percent by weightfrom batches containing the cerium concentrate of Ex- Na o; 1.52 percentby weight K 0; 0.17 percent by ample 1 have the following range ofingredients: weight Fe O 2.45 percent by weight Cr O and 3.67 percent byweight MnO.

Ingredients Weight Percent EXAMPLE 9 $10 45.4 53.56

Fe o 0.36 1.24 C O 0.49 0.71 As essentially colorless flint glass wasprepared for M go 0.10- 0.12 mixing with a frit prepared according tothe invention, 2 -5 22436 the batch materials for the flint glass wereas follows: (3:203 I 532 MnO 14.94 27.3 CeO 2.01 2.48 A1 0 0 0.41 IL8203 0 0.37 Ingredients Pounds F O 0.15 BaO O 0.08 222d h 1993.47 m0, 00.05 a as 380.48 Blast furnace slag 74.1 0

The foregoing ranges are based on Examples 1, 2 and 3. It will be seenfrom Examples 1, 2 and 3 that the ratio of MnO/Cr O ranges from 6.2 to13.6.

In the next three examples 10, l l, and 12, the ingredients employedwere as in Examples 1, 2 and 3, except that, oxides, for example, ceriumoxide, was employed for the abovestated ingredients. All glass-formingconditions were as described above.

EXAMPLE 1N WEIGHT PERCENT As will be seen from Examples 10, 11 and 12,the compositions of these three examples fall within the followingranges (in weight percent):

lngredients Weight Percent SiO 45.49 53.56 Fe o, 0.69 1.24 CaO 0.49 0.71MgO 0.10 0.12 Na O 18.97 22.86 K 1.21 1.46 C50 2.00 2.41 MnO 14.94 27.2CeO; 2.01 2.42

The ratio of MnO to Cr O in these three examples ranges from 6.2 to13.6.

It will be seen from all the examples in this case that the ratio of MnOto Cr O- is expressed as a weight percent ratio.

The invention has use for the fabrication of conventional articles likeglass jars, bottles, ash trays, tumblers and the like. And, whileoperative embodiments have been described herein in detail it is to beunderstood that modifications may be made without departing from thescope of the invention as set fourth in the specification.

I claim:

1. A colorant glass frit composition consisting essentially of thefollowing glass-forming oxides in the indicated percentages by weight:

Percent by Weight SiO 45.49 to 53.56 F6 0. 0.69 to 1.24 CaO 0.49 to 0.71MgO 0.10 to 0.12 N3 0 18.97 to 22.86 K 0 1.21 to 1.46 Cr o 2 to 2.41 MnO14.94 to 27.2 CeO 2.01 to 2.42.

2. A glass composition according to claim 1 wherein the glass consistsessentially of:

Percent by Weight $102 45.5 F6 0 1.24 C80 0.71 MgO 0.10 N8 0 18.97 K 01.21 10 2 6 MnO 27.2 C80; 2.01

and wherein the ratio of MnO to Cr O is 13.6 to 1.

3. A glass composition according to claim 1 wherein the glass consistsessentially of:

Percent by Weight SiO 1 0. CaO MgO Na O 2 K 0 Cr O MnO 2 CeO and whereinthe ratio of MnO to Cr O is 9.3 to l.

4. A glass composition according to claim 1 wherein the glass consistsessentially of:

Percent by Weight S10 53.6 F e 0 0.7 CaO 0.5 MgO 0.12 Na O 22.86 K 01.46 Cr O 2.41 MnO 14.9 CeO 2.4

and wherein the ratio of MnO to Cr O is 6.2 to 1.

5. A colorant glass frit composition consisting essentially of thefollowing glass-forming oxides in the indicated percentages by weight:

Percent by Weight 810 69.8 to 72.8 F6 0, 0.1 to 0.36 CaO 0.33 to 3.8 MgO0.16 to 0.19 Na O 18.26 to 21.57 K 0 1.2 to 1.52

Cr O 1.94 to 2.45 MnO 2.0 to 7.74 A1 0 0 to 006 wherein Cr O is added aspotassium dichromate and wherein the ratio of MnO to Cr O ranges from 1to 4.

6. A glass composition according to claim 5 wherein the glass consistsessentially of:

Percent by Weight $10 69.8 F6203 0.4 CaO 0.4 MgO 0. 16 Na- O 1 8.26 K201 .2 :1 1.94

MnO 7.74

and wherein the ratio of MnO to Cr O is 4 to 1.

7. A glass composition according to claim 5 wherein the glass consistsessentially of:

5 Percent by Weight SiO 72.8

Fe O 0.2

CaO 2. l

MgO 0. 1 7

Na o 1 879 K 1 .23 1 O Cr O 1 .99

MnO 3 .98

and wherein the ratio of MnO to Cr O is 2 to l.

8. A glass composition according to claim wherein the glass consistsessentially of:

Percent by Weight SiO 7 1 .74 F e 0 0. 1 2O CaO 3 M g0 0 Na O l 8. K 0 1Cr O 2 MnO 2 5 and wherein the ratio of MnO to Cr O is 1 to 1.

9. A glass composition according to claim 5 wherein the glass consistsessentially of:

Percent by Weight SiO; A1 0 CaO MgO Na O and wherein the ratio of MnO toCr O is 1.5 to 1.

10. A glass composition consisting essentially of the following oxidesin the indicated percentages by wei ht:

Percent by Weight and wherein the ratio of MnO to Cr O ranges from 6.2to 13.6.

11. A colorant glass frit composition consisting essentially of thefollowing oxides in the indicated percentages by weight:

$0; F e 0 CaO MgO Na O K 0 Cr O MnO CeO A1 0 La- O F BaO Pr O Nd O 45.4to 53.56 0.36 to 1.24 0.49 to 0.71 0.10 to 0.12 18.88 to 22.86 1.21 to1.50 2 to 2.43 14.94 to 27.3 2.01 to 2.48 0 to 0.41 0 to 0.37 0 to 0.150 to 0.08 0 to 0.05 0 to 0.17

and wherein the ratio of MnO to Cr O ranges from 6.2

12. A glass composition according to claim 10 wherein the glass consistsessentially of:

Si0 A1 0 Fe O CaO MgO Na O K 0 MnO CeO- Cr O L8 0. F

BaO mo. Nd o Percent by Weight 13. A glass composition according toclaim 10 wherein the glass consists essentially of:

SiO, A1 0 F e 0 CaO MgO Na O K- O MnO CeO Cr O La o F BaO Pr O Nd O 14.A glass composition according to claim 10 wherein the glass consistsessentially of:

SiO, A1 0 F5 0 CaO MgO Na O K 0 MnO CeO Cr- O La o F 8210 Pr O Nd oPercent by Weight UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATEOF CORRECTION.

PATENT NO. ,722

DATED Oct. 28, 1975 INVENTOR(S) A. 'L. Schaller It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Col. 12, line 42 (approximately) "CeO" should be CeO Signed and Sealedthis Third Day of May1977 [SEAL] A ttes t:

RUTH C. MASON C. MARSHALL DANN Arresting Office (ommr'sxinner ufPalenrsand Trademarks

1. A COLORANT GAASS FRIT COMPOSITION CONSISTING ESSENTIALLY OF THEFOLLOWING GLAS-FORMING OXIDES IN THE INDICATED PERCETAGE BY WEIGHT:
 2. Aglass composition according to claim 1 wherein the glass consistsessentially of:
 3. A glass composition according to claim 1 wherein theglass consists essentially of:
 4. A glass composition according to claim1 wherein the glass consists essentially of:
 5. A colorant glass fritcomposition consisting essentially of the following glass-forming oxidesin the indicated percentages by weight:
 6. A glass composition accordingto claim 5 wherein the glass consists essentially of:
 7. A glasscomposition according to claim 5 wherein the glass consists essentiallyof:
 8. A glass composition according to claim 5 wherein the glassconsists essentially of:
 9. A glass composition according to claim 5wherein the glass consists essentially of:
 10. A glass compositionconsisting essentially of the following oxides in the indicatedpercentages by weight:
 11. A colorant glass frit composition consistingessentially of the following oxides in the indicated percentages byweight:
 12. A glass composition according to claim 10 wherein the glassconsists essentially of:
 13. A glass composition according to claim 10wherein the glass consists essentially of:
 14. A glass compositionaccording to claim 10 wherein the glass consists essentially of: